Broadband optical cavity absorption spectroscopy in the near-ultraviolet: applications in atmospheric chemistry

A novel spectroscopic method, incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), has been modified and extended to measure absorption spectra in the near-ultraviolet with high sensitivity. The near-ultraviolet region extends from 300 to 400 nm and is particularly important in tropospheric photochemistry; absorption of near-UV light can also be exploited for sensitive trace gas measurements of several key atmospheric constituents. In this work, several IBBCEAS instruments were developed to record reference spectra and to measure trace gas concentrations in the laboratory and field. An IBBCEAS instrument was coupled to a flow cell for measuring very weak absorption spectra between 335 and 375 nm. The instrument was validated against the literature absorption spectrum of SO2. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably owing to the extremely weak absorption. The instrument was also applied to quantifying low concentrations of the short-lived radical, BrO, in the presence of strong absorption by Br2 and O3. A different IBBCEAS system was adapted to a 4 m3 atmosphere simulation chamber to record the absorption cross-sections of several low vapour pressure compounds, which are otherwise difficult to measure. Absorption cross-sections of benzaldehyde and the more volatile alkyl nitrites agree well with previous spectra; on this basis, the cross-sections of several nitrophenols are reported for the first time. In addition, the instrument was also used to study the optical properties of secondary organic aerosol formed following the photooxidation of isoprene. An extractive IBBCEAS instrument was developed for detecting HONO and NO2 and had a sensitivity of about 10-9 cm-1. This instrument participated in a major international intercomparison of HONO and NO2 measurements held in the EUPHORE simulation chamber in Valencia, Spain, and results from that campaign are also reported here.

Antenna tuning for wearable wireless sensors

When miniaturized wireless sensors are placed on or close to the human body, they can experience a significant loss inperformance due to antenna detuning, resulting in degradationof wireless performance as well as decreased battery lifetime.Several antenna tuning technologies have been proposed formobile wireless devices but devices suitable for widespread integration have yet to emerge. This paper highlights the possible advantages of antenna tuning for wearable wireless sensors and presents the design and characterization of a prototype 433MHz tuner module.

Broadband cavity-enhanced absorption spectroscopy with incoherent light

Although broadband incoherent light does not efficiently couple into a high-finesse optical cavity, its transmission is readily detectable and enables applications in cavity-enhanced absorption spectroscopy in the gas phase, liquid phase and on surfaces. This chapter gives an overview of measurement principles and experimental approaches implementing incoherent light sources in cavity-enhanced spectroscopic applications. The general principles of broadband CEAS are outlined and general “pros and cons” discussed, detailing aspects like cavity mirror reflectivity calibration or the establishment of detection limits. Different approaches concerning light sources, cavity design and detection schemes are discussed and a comprehensive overview of the current literature based on a methodological classification scheme is also presented.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Development of miniaturized antennas and adaptive tuning solutions for body sensor network applications

Wireless Sensor Networks (WSNs) are currently having a revolutionary impact in rapidly emerging wearable applications such as health and fitness monitoring amongst many others. These types of Body Sensor Network (BSN) applications require highly integrated wireless sensor devices for use in a wearable configuration, to monitor various physiological parameters of the user. These new requirements are currently posing significant design challenges from an antenna perspective. This work addresses several design challenges relating to antenna design for these types of applications. In this thesis, a review of current antenna solutions for WSN applications is first presented, investigating both commercial and academic solutions. Key design challenges are then identified relating to antenna size and performance. A detailed investigation of the effects of the human body on antenna impedance characteristics is then presented. A first-generation antenna tuning system is then developed. This system enables the antenna impedance to be tuned adaptively in the presence of the human body. Three new antenna designs are also presented. A compact, low-cost 433 MHz antenna design is first reported and the effects of the human body on the impedance of the antenna are investigated. A tunable version of this antenna is then developed, using a higher performance, second-generation tuner that is integrated within the antenna element itself, enabling autonomous tuning in the presence of the human body. Finally, a compact sized, dual-band antenna is reported that covers both the 433 MHz and 2.45 GHz bands to provide improved quality of service (QoS) in WSN applications. To date, state-of-the-art WSN devices are relatively simple in design with limited antenna options available, especially for the lower UHF bands. In addition, current devices have no capability to deal with changing antenna environments such as in wearable BSN applications. This thesis presents several contributions that advance the state-of-the-art in this area, relating to the design of miniaturized WSN antennas and the development of antenna tuning solutions for BSN applications.